EP2366731A1

EP2366731A1 - A process for preparing a composite material and composite material obtained

Info

Publication number: EP2366731A1
Application number: EP11158649A
Authority: EP
Inventors: Mauro Guzzini
Original assignee: DELTA Srl
Current assignee: DELTA Srl
Priority date: 2010-03-17
Filing date: 2011-03-17
Publication date: 2011-09-21
Anticipated expiration: 2031-03-17
Also published as: IT1398823B1; ITBO20100169A1; EP2366731B1

Abstract

A process is proposed for preparing a composite material that envisages the elimination of wetting, antibubble and thixotropic additives, while contemporarily providing the opportunity to increase the amount of inert filler in the finished product; according to this process a composition is polymerised comprising a resin, from 43 wt% to 75 wt% of particles of broken or alluvial quartz, which have a size from 0.1 mm to 2 mm, and from 3.25 wt% to 42 wt% of spheroidal particles, which have a spheroidal shape and a size smaller than 0.3 mm and are of glass.

Description

The present invention relates to a process for preparing a composite material and a composite material.
Although known manufactured products present good technical features, they meet only part of the current market needs. In particular, these manufactured products have an appearance, a tactile quality and physic-mechanical characteristics not always completely satisfactory for all uses and requirements of the most demanding consumers.
The patent EP1114716B1 describes manufactured products in composite material and a process for their preparation. The process described herein requires the use of additives for allowing proper molding of the manufactured products.
The aim of the present invention is to provide a process for preparing a composite material and a composite material that allow to overcome, at least partially, the disadvantages of the known art and are, at the same time, easily and economically produced.
According to the present invention, a process for preparing a composite material and a composite material are provided as cited in the independent claims below, and, preferably, in any of the claims which depend directly or indirectly from the independent claims.
Unless explicitly stated otherwise, the contents of references (articles, texts, patent applications, etc..) cited in this text is herein fully stated and described for completeness sake. In particular, the aforementioned references are incorporated herein by reference.
The invention is described below with reference to the attached drawing, which shows a non-limiting example of actuation, in which:

Figure 1 illustrates a stirrer usable in a method in accordance with the present invention.

According to a first aspect of the present invention a process for preparing a composite material is provided.
The process comprises a mixing step, during which a composition is mixed. The composition comprises from about 2 wt% to about 10 wt% of first inorganic particles, which have a size smaller than about 0.1 mm and comprise (in particular, consist of) a material selected from the group consisting of: silica, silicate; from 10 wt% to 30 wt% of an organic resin having a viscosity from 40 cps to 600 cps; from about 30 wt% to about 75 wt% of second inorganic particles, which have a size from about 0.1 mm to about 2 mm and comprise (in particular, consist of) silica; from about 3.25 wt% to about 42 wt% of third inorganic particles, which have a spheroidal shape and a size smaller than about 0.3 mm; from about 0.08 wt% to about 1 wt% of at least one silane having at least one vinyl moiety; and from about 1 wt% to about 6 wt% of at least one crosslinker; the sum of the weights of the first, second and third particles representing from about 65 wt% to about 85 wt% of the composition.
In the present text, unless explicitly stated otherwise, percentages by weight refer to the overall weight of the composition or composite material. For example, by stating that the composition comprises a percentage by weight of a particular component, it is intended that this percentage by weight is calculated with respect to the overall weight of the composition. Similarly, by stating that the composite material comprises a percentage by weight of a particular component, it is intended that this percentage by weight is calculated with respect to the overall weight of the composite material.
Advantageously, and unless explicitly stated otherwise, viscosity measurements are performed with a controlled rate rheometer, in particular with a Brookfield ® digital rheometer model DV-III RV following the standard instructions of its manual. The viscosity is measured at standard conditions (i.e. at room temperature -25°C - and a pressure of 1 atm).
Above 0.05 mm, for dimensions of the inorganic particles, the diameter of said particles is intended, extracted by successive sieving with decreasing sieve hole sizes down to 0.05 mm. Below 0.05 mm, for dimensions of the inorganic particles, the average diameter of said particles is intended, obtained in accordance with DIN 50049 / EN 10204 resulting in the specific surface area BET. In particular, the average diameter of the particles is calculated on the basis of the specific surface area BET (measured for example with a Micrometrics Tristar 3000 instrument) and a density (g/cm³). More specifically, the average diameter is calculated using the equation: $d = \frac{6000}{AS \times ρ}$
where d is the diameter in nm, AS is the surface area in m²/g, p is the density in g/cm³ (Song-Yuan Chang, Lei Liu, Sanford A. Asher, J. Am. Chem. Soc 1994, 116, 6745-6747; Zhijian Wu et al., Journal of Colloid and Interface Science, 304 (2006) 119-124).
To assess whether the particles have a spheroidal shape the greater diameter of a sample of fifty particles is measured by a scanning electron microscope with a graduated scale. It is estimated, therefore, the average greater diameter of these particles and this is compared with the average diameter calculated as described above (using the specific surface area BET). If the difference between the two average diameters is less than 15% (advantageously 10%) of the average greater diameter, particles shall be considered as spheroidal. On the contrary, if the difference between the two average diameters is greater than 15% (preferably 10%) of the average greater diameter, particles shall be considered as non-spheroidal.
The first and third particles can be equal or different to each other. In any case, the first and third particles are distinct entities. In other words, the amount (percentage by weight) of the first particles is not (and cannot be) considered as the amount (percentage by weight) of the third particles, and vice versa. The sum of the weights of the first and third particles is (therefore) in all cases from 5.25 wt% to 52 wt% of the composition. In other words, the sum of the weights of the first and third particles is (always) at least 5.25 wt% of the composition.
According to certain embodiments, the first and third particles are different from each other (i.e. differ in some certain aspects - for example, being of different dimensions and/or being made of different respective materials and/or being of different respective shapes from each other). In particular, the first particles do not have a spheroidal shape.
The process also includes a step of hardening (polymerisation), during which the organic resin hardens by reacting with the crosslinking agent resulting in the composite material. In particular, the organic resin polymerizes with the crosslinker.
In particular, the polymerisation step takes place after the composition is inserted into a mold.
According to certain embodiments, portions of inorganic particles are combined with the organic resin in successive moments. In these cases, aliquots of silane are combined with the organic resin at successive moments correspondingly to the particle portions. Each aliquot of silane is able to at least partially silanise the relative portion of particles. In this regard, it is important to underline that it has been experimentally observed that the silanisation capacity of silane has a limited duration (in particular, about twenty-four hours). Therefore, if the inorganic particles are added at different moments it is advantageous to add at different moments the corresponding amounts of silane, so that the silane can react.
It has been also experimentally observed that excessive amounts (higher than those needed to cover the surfaces of the inorganic particles) of silane increased the fragility of the composite material. Therefore, advantageously, the amount of silane is selected so that it can cover the surface of inorganic particles without however exceeding said aim.
According to certain embodiments, a first mixture is prepared by mixing, which includes the first particles, the organic resin and silane from 0.06 wt% to 0.15 wt% with respect to the overall weight of the first mixture. Subsequently, the first mixture, further silane, the second and third particles are combined together for obtaining said composition.
Advantageously, the composition includes at least 5 wt% of the first inorganic particles.
Note that it is experimentally observed that if the percentage by weight of the first particles is too low, compositions are obtained (which in reality are dispersions) being scarcely homogeneous and difficult to mould; if the percentage by weight of the first particles is too high, the composite material surface tends to be too glossy and the color tends to be monochromatic with less than optimal aesthetic results. Advantageously, the first particles have a size of at least 0.01. mm .
According to certain embodiments, the first inorganic particles comprise a material chosen from the group consisting of: cristobalite and wollastonite. In particular, the first inorganic particles are of a material chosen from the group consisting of: cristobalite and wollastonite.
According to certain embodiments, the first inorganic particles comprise silica. In particular, the first inorganic particles are of a siliceous material (silica).
According to certain embodiments, the organic resin is an acrylic resin, in particular a methacrylic resin.
Note that the viscosity of the resin identified above, allows improving the dispersion of inorganic particles within the resin itself. In this regard, it is to be underlined that insufficient viscosity causes uncontrollable decantation of the dispersion of the composition; high viscosity causes spotted or shiny surfaces on the manufactured product and compositions that tend to incorporate air.
According to certain embodiments, the resin comprises (in particular, consists of) at least one polymerisable organic monomer and at least one organic polymer. Advantageously, the composition consists of from 7 wt% to 37 wt% of the polymerisable organic monomer and from 2 wt% to 10 wt% of the organic polymer.
Advantageously, the composition comprises a percentage by weight of the polymerisable organic monomer less than about 24 wt%. According to certain embodiments, the composition comprises a percentage by weight of the polymerisable organic monomer greater than about 12 wt%.
According to certain embodiments, the polymerisable organic monomer comprises at least one acrylic monomer. In particular, the organic monomer is at least one acrylic monomer. More specifically, the organic monomer is an acrylic monomer. In other words, in these cases, the composition comprises from about 7 wt% to about 37 wt% of an acrylic monomer.
The acrylic monomer is selected from alkyl esters of acrylic or methacrylic acid, where alkyl has from one to six carbon atoms.
In particular, the acrylic monomer is chosen from the group consisting of: methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate. The composition may also comprise more than one type of acrylic monomers (for example, the composition may contain both MMA and ethyl methacrylate) in which case, the above percentages by weight of acrylic monomer with respect to the composition refer to the sum of the quantities of the different types of acrylic monomers.
Furthermore, in addition to the acrylic monomer/s, further polymerisable organic monomers may also be used, such as vinyl monomers like, for example, styrene, alpha-methyl styrene, acrylonitrile (see in this respect GB 1493393 ). In this case, the above percentages by weight of acrylic monomer with respect to the composition refer to the sum of the quantities of the acrylic monomer/s and of further monomers. The percentage by weight of vinyl monomers with respect to the overall weight of the acrylic monomer is, advantageously, less than 50 wt%.
According to certain embodiments, the polymerisable organic monomer includes at least one methacrylic monomer. In particular, the organic monomer is at least one methacrylic monomer. More specifically, the organic monomer is a methacrylic monomer. In other words, in these cases, the composition comprises from about 7 wt% to about 37 wt% of a methacrylic monomer.
The methacrylic monomer is selected from alkyl esters of methacrylic acid, where alkyl has from one to six carbon atoms.
In particular, the methacrylic monomer is selected from the group consisting of: methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, butyl methacrylate. The composition may also comprise more than one type of methacrylic monomers (for example, the composition may contain both ethyl methacrylate and MMA), in this case, the above percentages by weight of polymerisable organic monomer with respect to the composition refer to the sum of the quantities of the different types of methacrylic monomers.
According to specific embodiments, the polymerisable organic monomer is MMA.
Advantageously, the composition comprises a percentage by weight of organic polymer less than about 6 wt%. According to certain embodiments, the composition comprises a percentage by weight of organic polymer greater than about 3 wt%.
According to certain embodiments, the organic polymer has a molecular weight (PM_W) from 100X10³ to 150X10³.
According to certain embodiments, the organic polymer comprises (in particular, is) an acrylic polymer.
In the present text, acrylic polymer refers to a polymer obtained by polymerisation of at least one acrylic monomer as defined above. In particular, acrylic polymer refers to a polymer obtained by polymerisation of an acrylic monomer as defined above.
According to certain embodiments, the acrylic polymer is selected from the group consisting of: poly methyl methacrylate, poly ethyl methacrylate, methyl methacrylate-methyl acrylate copolymers, methyl methacrylate-styrene copolymers, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-methacryloxy propyl trimethoxy silane copolymers.
According to certain embodiments, the organic polymer comprises (in particular, is) a methacrylic polymer.
In the present text, methacrylic polymer refers to a polymer obtained by polymerisation of at least one methacrylic monomer as defined above. In particular, methacrylic polymer refers to a polymer obtained by polymerisation of at least one methacrylic monomer as defined above.
According to certain embodiments, the organic polymer is poly methyl methacrylate.
Advantageously, the composition comprises at least 43 wt% of the second inorganic particles.
Note that the second inorganic particles give hardness and resistance to the manufactured products, an excessive percentage by weight leads to compositions, which are scarcely homogeneous and tend to incorporate air.
According to certain embodiments, the second inorganic particles comprise (in particular, are) a siliceous material selected from the group consisting of; quartz, fused silica, milled glass. In particular, the second inorganic particles comprise (in particular, are) quartz. More specifically, the second inorganic particles comprise (in particular, are) alluvial or milled quartz.
Advantageously, the composition comprises at least 20 wt% of the third inorganic particles. According to certain embodiments, the composition comprises a percentage by weight of the third inorganic particles less than 30 wt%.
Note that the third inorganic particles improve homogeneity of the composition (which in reality is a dispersion), surprisingly allow to increase the concentration of inorganic particles and give the composite a soft satin surface to the touch. In addition, the third inorganic particles contribute, together with the silane, to increase the hardness of the surfaces.
Advantageously, the third inorganic particles have dimensions of at least 0.01 mm. According to certain embodiments, at least one third of the third inorganic particles is smaller than 0.05 mm.
Advantageously, the third inorganic particles comprise silica. In particular, the third inorganic particles are of a siliceous material. According to certain embodiments, the third inorganic particles comprise glass. In particular, the third inorganic particles are made of glass.
According to certain embodiments, the composition comprises from 0.1 wt% to 0.5 wt% of silane.
Note that, as already stated in part, a low percentage by weight of silane causes a shortage of bonds between the resin and the inorganic particles and therefore low physic-mechanical characteristics (the surface will dent easily and resistance to fading will drastically decrease), high amounts cause embrittlement of the composite material.
According to certain embodiments, the silane compound has at least one acrylic residue. In particular, the silane is an acryloxy trialcoxy silane. More specifically, the silane has the following structure,

A-Si-(OR)₃

where A represents an acrylic residue and R represents, each independently from the others, an alkyl, in particular a C₁-C₃ alkyl.
In the present text, unless specified otherwise, acrylic residue refers to a molecular portion comprising an acrylic or methacrylic group.
According to certain embodiments, the acrylic residue is selected from the group consisting of: methyl methacrylic, ethyl methacrilic, propyl methacrilic, butyl methacrylic, methyl acrylic, butyl acrylic. Advantageously, the acrylic residue is a methyl methacrylic group.
Unless the contrary is explicitly stated in the present text "Cx-Cy" refers to a group that is intended as a group presenting from x to y carbon atoms.
According to certain embodiments, A represents a methacrylic group. Advantageously, each R is methyl.
In particular, the methacrylic group is selected from the group consisting of: methyl methacrylic, ethyl methacrilic, propyl methacrilic, butyl methacrylic.
Advantageously, the silane is a 3-methacryloxytrimethoxysilane (MEMO). According to specific embodiments, the silane is A174 (distributed by Dynasylan MEMO) trimethoxysilyl-propyl methacrylate.
According to certain embodiments, the composition comprises from 2 wt% to 4 wt% of the crosslinker.
Note that small amounts of the crosslinker cause glossy surfaces with low resistance, high percentages cause cracking. According to certain embodiments, the crosslinker has at least two acrylic residues. In particular, the crosslinker presents at least two methacrylic groups.
According to certain embodiments, the crosslinker comprises at least one crosslinker with two vinyl moieties, in particular, methacrylic groups, and a crosslinker with three vinyl moieties, in particular methacrylic groups. Advantageously, the composition comprises from 0.5 wt% to 3 wt% of the crosslinker with two vinyl moieties, and at least 0.5 wt% to 3 wt% of the crosslinker with three vinyl moieties. In particular, the composition comprises from 0.5 wt% to 3 wt% of a crosslinker with two aryl residues, and at least 0.5 wt% to 3 wt% of a crosslinker with three aryl residues. More specifically, the composition comprises from 0.5 wt% to 3 wt% of the crosslinker with two methacrylic groups; and at least 0.5 wt% to 3 wt% of the crosslinker with three methacrylic groups.
According to certain embodiments, the crosslinker is selected from the group consisting of: ethylene glycol methacrylate (EGDM), triethylene glycol dimethacrylate (TEGDM), trimethylolpropane trimethacrylate (TMPTM), and mixtures thereof.
According to certain embodiments, the composition comprises a silanisation catalyst, which, in particular, is part of the first mixture.
The silanisation catalyst is selected from the group consisting of: methanol, isopropylamine, methacrylic acid and mixtures thereof.
Advantageously, the silanisation catalyst comprises methanol. In particular, the silanisation catalyst is methanol.
Advantageously, the silanisation catalyst comprises isopropylamine. In particular, the silanisation catalyst is isopropylamine.
According to certain embodiments, the step of polymerisation envisages the addition of a polymerisation initiator to the composition.
Advantageously, the initiator comprises (in particular, is) an additive selected from the group consisting of: lauryl peroxide, myristyl peroxydicarbonate, TBPEH (terbutyl-peroxy-2-ethylhexanoate), R913, bis (-terbutyl cyclohexyl) - peroxyocarbonate, and mixtures thereof. According to specific embodiments, the catalyst comprises (in particular, is) an additive selected from the group consisting of: lauryl peroxide, myristyl peroxy dicarbonate, bis (-terbutyl cyclohexyl)-peroxycarbonate and mixtures thereof.
According to specific embodiments, the catalyst is bis (-terbutyl cyclohexyl)-peroxycarbonate.
Advantageously, the composition comprises a release agent. According to certain embodiments, the release agent is selected from the group consisting of: zinc stearate, stearic acid, sodium dioctylsulphosuccinate or mixtures thereof. In particular, the release agent is zinc stearate.
Advantageously, completely absent in the composition are wetting, anti-bubble and/or thixotropic additives. According to certain embodiments the wetting, anti-bubble and/or thixotropic additives are: BYK W 969, BYK A 515, BYK 410 (all by BYK Chemie®).
According to a second aspect of the present invention, a composite material obtained by a process according to the first aspect of present invention is provided.
According to a third aspect of the present invention, a composite material obtainable by a process according to the first aspect of the present invention is provided.
According to a fourth aspect of the present invention (dependent or independent from the second and/or third aspect) a composite material is provided comprising from 2 wt% to 10 wt% of first inorganic particles, which have a size smaller than 0.1 mm and comprise a material selected from the group consisting of: silica, silicate, from 10 wt% to 30 wt% of a polymer matrix, from 30 wt% to 75 wt% of second inorganic particles, which have a size from 0.1 mm to 2 mm and comprise silica, and from 3.25 wt% to 42 wt% of third inorganic particles, which include silica and have a spheroidal shape and a size smaller than 0.3 mm. The second and third inorganic particles are at least partially bound to the polymer matrix by means of covalent bonds. The sum of the weights of the first, second and third particles representing from 65 wt% to 85 wt% of the composite material.
The first, second and third inorganic particles are defined, independently of each other, as indicated above in accordance with the first aspect of the present invention.
According to certain embodiments, the composite material comprises percentages by weight of the first, second and third inorganic particles identical to those listed above for the composition with reference to the first aspect of the present invention.
Advantageously, the first inorganic particles are at least partially bound to the polymer matrix by covalent bonds.
In particular, the polymer matrix is bound to the first, second and third inorganic particles by Si-O-Si bonds.
According to certain embodiments, the polymer matrix includes (in particular, is) an acrylic polymer.
According to certain embodiments, the polymer matrix comprises a methacrylic polymer. In particular, the polymer matrix is a methacrylic polymer. More specifically, the polymer matrix is of polymethylmethacrylate.
Advantageously, the polymer matrix is at least partially crosslinked.
According to a further aspect of the present invention a manufactured product comprising the mentioned composite material (defined in accordance with the fourth aspect of the present invention) is provided. Examples of manufactured products comprising the mentioned material are: kitchen sinks, bathroom sinks, washbasins for public places, bathroom work tops, kitchen work tops, counter tops, thermoformed flat slabs, walls, ceilings, bathtubs, bathroom accessories, shower basins, shower walls and shower stalls.
According to a further aspect of the present invention a composition as defined above is provided.
Importantly to be noted is that the subject of the present invention presents the following advantages with respect to the state of the art:

reduction of viscosity (of the composition), with equal solid content in the dispersion (about 70%), from about 9000 cps to 5000 cps;
possibility for increasing the content of inert filler;
possible elimination of all wetting and antibubble additives;
possible elimination of thixotropic additives, being particularly surprising that by adding a particular filler, such as glass beads, which do not have thixotropic properties, the total elimination of these additives is obtained, with significant benefits on the process, the stability of the dispersion and the cost (see specific examples).

Additional features of the present invention will be clear from the following description of certain merely illustrative and non restrictive examples.

Example 1

Preparation of a neutral intermediate (first mixture)

This preparation can be carried out according to specific needs by working with a wide range of quantities. In an example of actuation the preparation has followed the indications of the patent EP1114716B1 and, in particular, has followed the procedure given below.
In a 1000cc container of high density polyethylene using a Velp rod stirrer with a Cowles impeller (600-1000 rpm) were mixed:

570 grams of high purity methyl methacrylate
150 grams of methyl methacrylate beads PM_W = 100 - 150 10³ ; diameter = 100-200 microns

The mixture was stirred until complete dissolution of the beads.
Then were further added:

28 grams of crosslinking agents EGDM - TEGDM - TMPTM;
1 gram of silane A174 trimethoxysilyl - propylmethacrylate;
250 grams of cristobalite B0012 Sihelco®.

As catalysts of silanisation variable amounts of mixtures of methacrylic acid and isopropylamine from 0.7 to 1.2 grams were used.

Example 2

Laboratory preparation of a composite material

In a 1000cc container of high density polyethylene by using a Velp rod stirrer with a blade impeller (600-1000 rpm) were mixed:

308.5 grams of neutral of example 1;
480 grams of quartz from Lucchi Granulati® (Verona);
69 grams of solid glass micro-beads with a particle size of 0-50 microns from Elettrochimica Vallestaffora ® (Rivanazzano PV);
138 grams of solid glass micro-beads with a particle size of 63-212 microns from Elettrochimica Vallestaffora (Rivanazzano PV);
1.5 grams of color paste;

The mixture was dispersed vigorously by the use of the rod stirrer adding 5 grams of bis(4-terbutylciclohexyl)-peroxydicarbonate and 2.5 grams of stearic acid.
The mixture was placed between two sheets of nickel-plated steel, closed by a gasket of plasticized PVC in order to obtain a composite sheet on which to carry out characterization. The curing of the sheet was obtained by heating the mold in hot a bath at 65° C for 40 minutes.

From the mold, properly cooled, a sheet was obtained that has the characteristics shown in Tables 1-4. The tables also indicate the measurement methods used with regard to the relative UNI standards.

Table 1

Rockwell Hardness HRM UNI EN ISO 2039-2:2001	Charpy KJ/m² UNI EN ISO 179-01:2002	Modulus of elasticity in bending (MPa) UNI EN ISO 178	Flexural strength (MPa) UNI EN ISO 178
109	3.9	11,570	83

Table 2

Scratch resistance scratch depth at 20 N (µm) UNI EN 13310:2004	Taber Abrasion UNI ISO 9352:1999	Thermal Shock UNI EN 13310:2004
139	78	1000 cycles ok Delta E=2,5

Table 3

SURFACE RESISTANCE TO DETERGENTS FOR DOMESTIC USE UNI EN 14527:2006
	Assessment and Compliance
*Product*	*After rinsing with water*	*water Cleaning with sponge*
1. Lisoform Bagno Gel	C	C
2. Viakal	C	C
3. cif crema	C	C
4. Bleaching solution	C	C
5. Ammonia	C	C
6. Alcohol	C	C
7. Multi Purpose (Glassex)	C	C

Tabella 4

SURFACES RESISTANCE TO CHEMICAL SUBSTANCES AND STAINING AGENTS UNI EN 13310:2004
		Assessment and Compliance
*Family*	*Product*	*After rinsing with water*	*Cleaning with water with sponge*	*Cleaning with allumina 12-h with sponge*
*Acids*	1. Acetic acid (CH₃COOH), 10% V/V	C	C	C
*Alkali*	2. Caustic soda (NaOH), 5% m/m	C	C	C
*Alcohol*	3. Ethanol (C₂H₅OH), 70% V/V	C	C	C
*Bleaching agents*	4. Sodium hypochlorite (NaOCl), 5% active chlorine (Cl₂)	C	C	C
*Dyes*	5. Methylene blue, 1% m/m	C	C	C
*Salts*	6. Sodium chloride (NaCl), 170 g/l, diluted to 50 %	C	C	C

In Tables 3 and 4, C indicates conform and ND indicates not conform.
As can be noted from the above tables, the material surprisingly resists all agents.

Example 3

Preparation of a neutral intermediate (first mixture)

In a 8 mc reactor of stainless steel fitted with a blade stirrer (80-200 rpm) are loaded:

2850 kg of high purity methyl methacrylate;
750 kg of methyl methacrylate beads PM_W = 100 - 150 10³; diameter = 100 - 200 microns.

The mixture was stirred until complete dissolution of the beads.
Then are further added:

138 kg of crosslinking agents such as EGDM - TEGDM - TMPTM;
5 kg of silane A174 trimethoxysilyl - propylmethacrylate;
1250 kg of cristobalite B0012 Sihelco®.

As catalysts of silanisation variable amounts of mixtures of methacrylic acid and isopropylamine from 3.5 to 6 kg were used.

Example 4

Industrial preparation of the composite material

In a 1.2 mc cylindrical shaped reactor with a diameter/height ratio of about 1, fitted with a stainless steel stirrer (see Figure 1) (the stirrer operates within a speed range between 5 and 90 rpm) were loaded:

493 kg of the neutral mentioned in example 3;
772 kg of quartz by Lucchi Granulati® (Verona);
110.4 kg of solid glass micro-beads with a particle size of 0-50 microns by Elettrochimica Vallestaffora® (Rivanazzano PV);
220.8 kg of solid glass micro-beads with a particle size of 63-212 microns by Elettrochimica Vallestaffora® (Rivanazzano PV);
2.4 kg of color paste;
2.4 kg of silane A174 trimethoxysilyl - propylmethacrylate; The mixture was dispersed with the above indicated reactor that was ready to supply the molding container where the dispersion will be catalised in the mode already described in Example 2, taking into account the different amounts considered.

Example 5

Semi-industrial scale tests

In order to expect significant results three sinks were prepared (using 40 kg of material), upon which the various different measurements were repeated, the result of which, reported below, are average values.
It was loaded:

12.30 kg of the neutral mentioned in example 3;
19.30 kg of quartz by Lucchi Granulati® (Verona);
2.76 kg of solid glass micro-beads with a particle size of 0-50 microns by Elettrochimica Vallestaffora ® (Rivanazzano PV);
5.52 kg of solid glass micro-beads with a particle size of 63-212 microns by Elettrochimica Vallestaffora® (Rivanazzano PV);
60 g of color paste;
60 g of silane A174 trimethoxysilyl - propylmethacrylate.

The dispersion was placed in 30-liter cylindrical containers that were rolled for 8 hours for achieving the maximum redispersion of the mixture.
The dispersion thus obtained was poured into the molding container where the dispersion was catalysed in the mode already described in the example 2 above.

From the molding process a sink is obtained with the characteristics indicated in the following tables 5-8. Indicated in the tables are also the measurement methods used with regard to the relevant UNI standards.

Table 5

Rockwell Hardness HRM UNI EN ISO 2039-2:2001	Charpy KJ/m² UNI EN ISO 179-01:2002	Modulus of elasticity in bending (MPa) UNI EN ISO 178	Flexural strength (MPa) UNI EN ISO 178
113	4.5	12,450	86

Table 6

Scratch resistance scratch depth of 20 N (µm) UNI EN 13310:2004	Taber Abrasion UNI ISO 9352:1999	Thermal Shock UNI EN 13310:2004
139	78	1000 cycles ok Delta E=2.5

Table 7

SURFACE RESISTANCE TO DETERGENTS FOR DOMESTIC USE UNI EN 14527:2006
	I *Assessment and Compliance*
*Product*	After rinsing with water	**Cleaning water with sponge**
1. Lisoform Bagno Gel	C	C
2. Viakal	C	C
3. Cif crema	C	C
4. Bleaching solution	C	C
5. Ammonia	C	C
6. Alcohol	C	C
. Multi Purpose (Glassex)	C	C

Table 8

SURFACE RESISTANCE TO CHEMICAL SUBSTANCES AND STAINING AGENTS UNI EN 13310:2004
		*Assessment and Compliance*
*Family*	*Product*	*After rinsing with water*	*Cleaning with water with sponge*	*Cleaning with allumina 12-h with sponge*
*Acids*	1. Acetic acid (CH₃COOH), 10% V/V	C	C	C
*Alkali*	2. Caustic soda (NaOH), 5% m/m	C	C	C
*Alcohol*	3. Ethanol (C₂H₅OH), 70% V/V	C	C	C
*Bleaching agents*	*4. Sodium hypochlorite (Naocl), 5% active chlorine (Cl₂)*	C	C	C
*Dyes*	5. Methylene blue, 1% m/m	C	C	C
*Salts*	**6. Sodium chloride (NaCl), 170 g/1, diluted to 50 %**	C	C	C

In Tables 7 and 8, C indicates conform and ND indicates not conform. As can easily be seen from the above data the products have surprisingly passed all the tests.

Example 6

Tests with additives

In the modes already described in example 5, 4 formulations of 40 kg of dispersion, referred to as formulation A, B, C and D were prepared.
The formulation A is free of any additives and is taken as a reference.
The formulation B, before being molded is charged with a wetting additive (BYK W968 by BYK Altana group) in a percentage of 0.3 wt%. The next step is the molding process as in formulation A.
The formulation C, before being molded is charged with an antibubble additive (BYK A515 by BYK Altana group) in a percentage of 0.3 wt%. The next step is the molding process as in formulation A.
The formulation D, before being molded is charged with a thixotropic additive (BYK 410 by BYK Altana group) in a percentage of 0.2 wt%. The next step is the molding process as in formulation A.

The results of thermal shock tests are shown in Table 9 below.

Table 9

Formula	Article characteristics	Thermal Shock (15°C - 90°C)
A	Homogeneous material with no stains, no holes or cracks, smooth and very compact surface	1000 cycles ok Bleaching: delta E = 1.5
B	scarcely homogeneous material, streaks on the bath tub walls	at 700 cycles the piece broke
C	Same as B	at 800 cycles the piece broke
D	scarcely homogeneous material with glossy spots and low sedimentation. Presence of holes	at 600 cycles the piece broke

From the obtained results, it can be observed that surprisingly the addition of additives not only does not lead to any substantial benefit but rather to a deterioration in material characteristics.

Example 7

Comparison of viscosity

7.1 Preparation of intermediate Neutral (first mixture)

In a 1000cc container of high density polyethylene by using a Velp rod stirrer with a Cowles impeller (600-1000 rpm) were mixed:

570 grams of high purity methyl methacrylate;
150 grams of methyl methacrylate beads PM_W = 100 - 150 10³ diameter = 100-200 microns.

The mixture was stirredd until complete dissolution of the beads.
Then are further added:

12 grams of fumed silica;
14 grams of crosslinking agents EGDM - TEGDM;
5 grams of silane A174 trimethoxysilyl - propylmethacrylate;
250 grams of cristobalite B0012 Sihelco®.

Silanisation Catalysts were used in various amounts of mixtures of methacrylic acid and isopropylamine from 0.7 to 1.2 grams.

7.2 Preparation of a dispersion (composition) not actuated in accordance with the present invention

365 grams of the produced neutral (as in example 7.1 above);
617.4 g of quartz from by Lucchi Granulati® (Verona);
2 grams of color paste;

The mixture was dispersed vigorously by the use of the rod stirrer by adding:

3 grams of BYK W969;
3 grams of BYK A515;
1 gram of BYK 410.

The viscosity of the dispersion thus obtained was measured with a Brookfield viscometer model DV-III RV. The results are shown in Table 10: Table 10

Speed Torque Viscosity Temp. °C

2 5.5 11000 25

4 9.7 9700 25

10 19 7600 25

20 31.3 6260 25

7.3 Preparation of a dispersion (composition) actuated in accordance with the present invention

365 grams of neutral as in example 1;
432.2 g of quartz by Lucchi Granulati® (Verona);
61.7 grams of solid glass micro-beads with a particle size of 0-50 microns by Elettrochimica Vallestaffora® (Rivanazzano PV);
123.5 grams of solid glass micro-beads with a particle size of 63-212 microns by Elettrochimica Vallestaffora ® (Rivanazzano PV);
2 grams of color paste;
1.5 grams of silane A174 trimethoxysilyl - propylmethacrylate;

The mixture is dispersed vigorously by the use of the rod stirrer.
The viscosity of the dispersion thus obtained was measured with a Brookfield viscometer model DV-III RV. The results are shown in Table 11: Table 11

Speed Torque % Viscosity Temp. °C

2 2.5 5000 25

4 4.7 4700 25

10 10.4 4160 25

20 18.9 3780 25
As can be easily seen, the properties of the dispersion mentioned in example 7.3 are surprisingly and significantly better than those of the dispersion of the example 7.2.

Example 8

Molding test of a material in accordance with the present invention

A verification was made on the characteristics of molding a dispersion formulation with increased charge (with percentage of inorganic particles close to that of examples 2 and 4 above). The tests were repeated in order to mold three sinks.
From preliminary tests in the laboratory it was found that increasing the charge for more than 65% the quartz was not wet enough to be managed in production.
It was loaded:

14 kg of the neutral as in example 7.1;
26 kg of quartz by Lucchi Granulati ® (Verona);
80 g of color paste;
120 grams of BYK W969;
120 grams of BYK A515;
40 grams of BYK 410;

The dispersion was placed in 30-liter cylindrical containers that were rolled for 8 hours so as to achieve maximum redispersion of the mixture. The dispersion thus obtained was poured into the molding container where the dispersion was catalysed in the modes already described in Example 2 above.
There were major complications during the injection, the material transited with great difficulty to exit the injection tube. The obtained sinks presented many holes due to trapped air. The three obtained sinks were considered non-recoverable waste.
By comparing actual results with those described in examples 2 and 4, it can be noted that the behavior of the dispersions and the characteristics of the material of the examples 2 and 4 are astonishing improvements.

Claims

A process for preparing a composite material; the method comprises:
a mixing step, during which a composition is mixed; the composition comprising from 2 wt% to 10 wt% of first inorganic particles, which have a size smaller than 0.1 mm and comprise a material selected from the group consisting of: silica, silicate; from 10 wt% to 30 wt% of an organic resin having a viscosity from 40 cps to 600 cps; from 30 wt% to 75 wt% of second inorganic particles, which have a size from 0.1 mm to 2 mm and comprise silica; from 3.25 wt% to 42 wt% of third inorganic particles, which have a spheroidal shape and a size smaller than 0.3 mm; from 0.08 wt% to 1 wt% of at least one silane having at least one vinyl moiety; and from 1 wt% to 6 wt% of at least one crosslinker; the sum of the weights of the first, second and third particles forming from 65 wt% to 85 wt% of the composition;

a polymerizing step, during which the organic resin polymerises together with the crosslinker so as to obtain the composite material.
The process according to claim 1, wherein the composition comprises at least 5 wt% of the first inorganic particles and at least 43 wt% of the second inorganic particles.
The process according to claim 1 or 2, wherein portions of inorganic particles are combined with the organic resin at subsequent times; aliquots of the silane being combined with the organic resin at subsequent times correspondingly to the portions of particles; each aliquot of silane silanising the corresponding portion of particles at least partially.
The process according to one of the preceding claims, wherein a first mixture, which comprises the first particles, the organic resin, and from 0.06 wt% to 0.15 wt%, with respect to the overall weight of the first mixture, of silane, is prepared by mixing; subsequently, the first mixture, additional silane, the second and third particles are combined together so as to obtain said composition.
The process according to one of the preceding claims, wherein the cross-linker has at least two acrylic residues; the silane has at least one acrylic residue.
The process according to one of the preceding claims, wherein
the crosslinker comprises at least one crosslinker with two vinyl moieties, in particular two acrylic residues, and a crosslinker with three vinyl moieties, in particular two acrylic residues; the composition comprising from 0.5 wt% to 3 wt% of the crosslinker with two vinyl moieties; and at least 0.5 wt% to 3 wt% of the crosslinker with three vinyl moieties;
the silane is an acryloxy trialcoxy silane having, in particular, the following structure,
A-Si-(OR)₃
wherein A represents an acrylic residue and R each independently represents an alkyl, in particular a C₁-C₃ alkyl.
The process according to one of the preceding claims, wherein the organic resin is a methacrylic resin.
The process according to one of the preceding claims, wherein the organic resin consists of at least one polymerisable organic monomer and at least one organic polymer; the composition comprising from 7 wt% to 37 wt% of the polymerisable organic monomer and from 2 wt% to 10 wt% of the organic polymer.
The process according to claim 8, wherein the polymerisable organic monomer comprises at least one acrylic monomer; the organic polymer comprises at least one acrylic polymer.
The process according to claim 9, wherein the polymerisable organic monomer is a methacrylic monomer; the organic polymer is a methacrylic polymer; the crosslinker has at least two methacrylic groups; the silane has at least one methacrylic group.
The process according to claim 10, wherein the polymerisable organic monomer is methyl methacrylate; the organic polymer is polymethyl methacrylate; the crosslinker is selected from the group consisting of: ethylene glycol methacrylate (EGDM), triethylene glycol dimethacrylate (TEGDM), trimethylolpropane trimethacrylate (TMPTM) and mixtures thereof; the silane is a 3-methacryloxytrimethoxysilane.
The process according to one of the preceding claims, wherein the composition comprises a silanisation catalyst, which, in particular, is part of the first mixture; the step of polymerisation provides that a polymerisation initiator is added to the composition.
The process according to one of the preceding claims, wherein the third inorganic particles are made of siliceous material; the second inorganic particles are made of a siliceous material selected from the group consisting of: quartz, fused silica, glass; the first inorganic particles are made of a material selected from the group consisting of: cristobalite, wollastonite.
The process according to one of the preceding claims, wherein the first inorganic particles comprise silica and the third inorganic particles are made of glass.
The process according to one of the preceding claims, wherein the first and third inorganic particles have a size of at least 0.01 mm; at least one third of the third particles have a size smaller that 0.05 mm.
A composite material comprising from 2 wt% to 10 wt% of first inorganic particles, which have size smaller than 0.1 mm and comprise a material selected from the group consisting of: silica, silicate; from 10 wt% to 30 wt% of a polymer matrix; from 30 wt% to 75 wt% of second inorganic particles, which have a size from 0.1 mm to 2 mm and comprise silica; and from 3.25 wt% to 42 wt% of third inorganic particles, which have a spheroidal shape and a size smaller than 0.3 mm and comprise silica; the second and third inorganic particles being at least partially bound to the polymer matrix by means of covalent bonds; the sum of the weights of the first, second and third particles forming from 65wt% to 85wt% of the composite material.
The composite material according to claim 16, and comprising at least 5 wt% of the first inorganic particles and at least 43 wt% of the second inorganic particles.
The composite material according to claim 16 or 17, wherein the first inorganic particles comprise silica and are at least partially bound to the polymer matrix by means of covalent bonds; the polymer matrix comprising an acrylic polymer.
The composite material according to one of claims 16 to 18 wherein the polymer matrix consists of an acrylic polymer; the third inorganic particles are made of glass; the second particles are made of a siliceous material selected from the group consisting of: quartz, fused silica, milled glass; the first particles are made of a material selected from the group consisting of: cristobalite, wollastonite.
The composite material according to one of claims 16 to 19, wherein the first and third inorganic particles have a size of at least 0.01 mm; the polymer matrix being partially methacrylic; at least one third of the third particles having a size smaller that 0.05 mm.
The material according to one of claim 16 to 20, obtained according to the process of one of claims 1 to 15.
A product comprising a material according to one of claims 16 to 21.